Laser manufacturing of aluminum and titanium alloys is gaining interest in the automotive, aerospace, and defense industries due to its diverse applications. Laser interaction with these alloys involves heating, melting, and evaporation, with evaporation being critical. Selective vaporization of certain elements in multi-element alloys can affect stoichiometry. In-situ monitoring of the ejected plume helps control the product quality. Optical emission spectroscopy (OES) characterizes the plume constituents and provides information about the excited states. Our study uses high-speed imaging (HSI) and OES to monitor the laser interaction process with AlMg5 and Ti6Al4V alloys. OES analysis reveals a higher rate of magnesium evaporation compared with aluminum during the millisecond laser interaction with AlMg5, a trend that intensifies with an increase in laser power and a decrease in speed. On the other hand, the selective evaporation of magnesium in comparison with aluminum during the nanosecond laser interaction with the AlMg5 alloy is negligible, indicating no effect on stoichiometry. During the interaction between the millisecond laser and the Ti6Al4V alloy, titanium is found to evaporate more compared with aluminum, despite the higher boiling point of titanium relative to aluminum. This behavior contrasts with that of the AlMg5 alloy. HSI reveals an increase in spatter and laser-plume interaction with increased laser power and decreased speed during millisecond laser interaction with AlMg5. In-situ monitoring during single-shot millisecond laser interactions is conducted in a controlled manner with and without Ar gas shielding. The detection of oxidation in the absence of shielding gas through OES analysis highlights its potential for process monitoring.